Separation of nickel and cobalt metal from acidic solution



Nov. 9, 1954 F. A. SCHAUFELBERGER SEPARTION OF NICKEL AND COBALT METAL FROM ACIDIC SOLUTION Filed March 14, 1952 ATTORNEY United States Patent() SEPARATION OF NICKEL AND COBALT METAL FROM ACIDIC SOLUTION Felix A. Schaufelberger, Yonkers, N. Y., assignor to Chemical Construction Corporation, New York, N. Y., a corporation of Delaware Application March 14, 1952, Serial No. 276,711

19 Claims. (Cl. 75-108) vThis invention relates to the hydrometallurgy of nickel and cobalt. More specifically, it is concerned with the selective separation of cobalt and nickel from aqueous solutions containing dissolved salts of both. Still more specically, it involves a new method capable of severally collecting cobalt and nickel as a metal powder, each substantially free of the other, from solutions containing soluble salts of both.

Nickel and cobalt metals are very similar in many physical and chemical characteristics. The same is true of their salts and naturally-occurring minerals. Moreover, minerals of both generally occur together in natural deposits and usually cannot be separated by ordinary mineral dressing practices. For these reasons, both metals are generally present, in varying amounts, in any solution resulting from any type of leaching of materials containing cobalt and nickel.

This results in many technical and economic problems. For example, in most ordinary practices, small amounts of cobalt present in nickel ore concentrates represent little of benefit to the nickel producer. Very little cobalt available in such materials is recovered and sold as such, primarily because by current methods the cost of separation equals or exceeds the additional value. Much, if not most of the cobalt is lost in the slag from nickel smelting. The remainder is sold as nickel in nickel metal bullion or cathodes.

Similarly, small amounts of nickel present in cobalt concentrates, and therefore, in the cobalt solutions after leaching, is of small value. It is generally either discarded, a considerable loss, or is recovered with the cobalt In the latter case, the nickel becomes an impurity in the cobalt metal and generally the producer is not paid for it. While certain nickel and cobalt mixed metals are marketable as such, it is usually at a price below the value of the pure metals in separate products.

In conventional metallurgy of nickel and cobalt, then, the presence of smaller but appreciable quantities of either in sources of the other, i. e., in ores, ore concentrates, scrap metals, plant by-products and the like, presents a serious and ditiicult problem. This problem has heretofore been variously attacked. However, a generallypracticable treatment whereby the bulk of each may be recovered in a separate, relatively-pure metal product has not been offered.

Many processes have been proposed for separation and recovery of cobalt and nickel from mixed electrolytes. Several have been used quite extensively. Most involve the same two facts, that cobalt is more readily oxidized to the trivalent state than is nickel and that cobaltic hydroxide is relatively more insoluble at lower pH values than is nickelous hydroxide. Unfortunately, the necessary steps are complicated and repetitive, the hydroxides are difficult to lter efficiently and the resultant separations are far from perfect. Moreover, most of them also require large quantities of chemical reagents, many of which are non-regenerative. In addition to the elfect on costs, this creates a disposal problem.

Several methods of separating nickel and cobalt from ammonium carbonate leach liquors also have been proposed. ln general they involve fractional distillation of the ammonium carbonate. Liquor, at different stages in the process, thereby becomes concentrated with either nickel or cobalt by precipitation of the other as hydrated oxides. Concentrated liquor is removed and treated. The precipitates must be redissolved and retreated. However, as processing methods or as to nal products, these are economically and practically little better than the electrolyte treatments.

Such conventional processes for the production of nickel or cobalt products, then, are commercially unsatisfactory as too complicated, wasteful or uneconomical or as resulting in products containing undesirably large amounts of the other element. Neither do they produce saleable metals. The resultant oxides or hydroxides must be processed further to obtain this result.

It is, therefore, the principal object of this invention to provide an improved method capable of separate precipitation of cobalt and nickel from solutions containing salts of both. Such a method should not be subject to the objections to prior practice. Both metals should be economically recovered in acceptable quantity and quality. Such a process should require only the use of commonly-available chemical reagents and preferably only those which may be either regenerated or recovered in the form of valuable by-products.

Surprisingly, the desired objects of the present invention have been achieved in an effective manner in a simple, economical process. A general outline of the separation process may be simply described. An aqueous acid solution, containing cobalt, nickel and usually ammonium salts of the acid, is adjusted to the correct degree of acidity and dilution. Sulfuric acid will be the acid that is most commonly encountered. This `solution is then treated with a reducing gas at elevated temperatures and controlled acidity conditions. A succession of such treatments, at differing but controlled conditions, precipitates a successive series of products which are separately collected. The rst product will usually comprise high-purity nickel metal powder, the last will comprise a substantially nickel-free cobalt metal powder.

Salts, such as the sulfates, of certain metals, such as nickel or cobalt, when dissolved in water produce inherent pH conditions at which the metal cation cannot be practically reduced to metal with a reducing gas. If the solution is then partly neutralized with some noncomplexing base such as sodium hydroxide, reduction to metal can be initiated. However, as the reduction proceeds the solution quickly becomes more acid and reaction stops.

In the novel procedure of my copending application with P. l. McGauley, Serial No. 276,716, iled of even date, it has been shown how this diflicultyfmay be overcome and that a salt of either nickel or cobalt, in an acid solution free of the other, can be reduced quickly and completely to a metal powder with a gas such as hydrogen, at elevated temperatures, in the presence of a compatible electrolyte and at controlled conditions of acidity. According to the present invention, it has been found further that this reduction can be made to'operate and can be controlled to selectively precipitate nickel from cobalt when salts of both are present.

In the present process, much more than the simple reduction of a single metal from solution is required. Precipitation must be of the metal itself. It must be substantially completely recovered. It must be recovered in commercially acceptable purity. It must be in useful condition, i. e., as a useful, easily-collected product and not as a deposit on the wall of the reduction vessel. It must be a powder, free from occlusions and suitable for further metallurgical use when washed and dried.

Primarily, however, the cobalt-nickel separation must be effective. The nickel product should not contain more than about G25-0.50% by weight of cobalt. The cobalt product usually should be equally free from nickel.

It is believed that the invention may be more readily understood with reference to the accompanying drawing. In the latter is delineated a simplified liow diagram showing one useful embodiment of the invention.

Certain factors should be noted before further discussion. The present process often may comprise a part of an overall treatment of a nickel-cobalt-copper ore.

Processes are known for the elimination or recovery of such extraneous constituents as iron, arsenic, excess sulfur, insoluble gangue, zinc, lead, gold, silver and the like, therefrom. Methods are also known for leaching the l resultant concentrates to convert the nickel and cobalt minerals, usually also together with any copper in the ore, to a mixture of soluble or solubilizableproducts, usually salts. Any of these known procedures may be the source of the materials to be treated here. Copper, 1f present,

will constitute a valuable product. Much or all of it will 5 have been removed before the materials come to the present process. Except to the extent that such known processees may serve as sources of the soluble or solubilizable cobalt and nickel-bearing materials to be treated here, this invention is not concerned therewith.

The nature and source of the cobalt and/ or nickel-bearing materials to be treated according to the present process may be widely varied. They will, however, comprise either soluble metal salts, usually sulfates, or compounds easily converted thereto. They may be in solid form or in solution. In the latter case, some purification may be desirable, i. e., filtering, crystallization, redissolving and the like. If solids are to be dissolved, an aqueous acid is usually preferable, since, as will be seen, the nickel precipitation steps must end and will usually start under acidic conditions.

Many if not most of the ore concentrates treated in the above-noted overall process will be suldic. In many of the known leaching treatments sulfuric acid will be either used or formed. In such cases the products treated here will usually be sulfates. The sulfate anion is a de sirable one throughout the present process. Other conventional leaching processes produce nickel or cobalt oxides, hydroxides and carbonates. These are easily taken up in sulfuric acid solutions. Where it is not alreadyl present, sulfuric acid usually is still the most practical and economical one. However, separation by selective reduction can be made using other polybasic inorganic acids such as phosphoric, uosilic and the like whose second hydrogen ion has a low degree of ionization comparable to sulfuric. Much more care is required to prevent metal salts of these acids from coming out of solution. Highly ionizable monobasic inorganic acids such as nitric and the hydrohalides are not usefully operable in the present process. Certain monobasic organic acids such as formic and acetic may be used. Formic acid may be used, at least in part, as a reducing agent. Sulfuric acid, however, will be taken as illustrative, in this discussion as being that most used and economical.

Where in the present specification and claims the terms free acid or uncombined acid are used they refer` to the stoichiometric excess of anions over the sum of the metal and the ammonium cations. Unless otherwise noted, they will refer to sulfate ions. Similarly, Where hydrogen ion concentration at stated strengths of acid or free acid the hydrogen ion concentration of aqueous sulfuric acid of the stated strength is intended.

The solution operation shown, in the owsheet, therefore, may be done specifically for this process or may have occurred in some prior treatment. The actual formation of the solution to be treated, except as to the adjustment of its dissolved content, does not constitute a patentable feature of the invention and therefore has been indicated in light lines in the drawing.

Since, as noted, the prior treatment may have involved a copper recovery, there may be some residual copper in the salts, or solution of salts, coming to this process. If so, it should be removed from solution prior to cobalt and nickel recovery. This may be done in any desired manner. One of the simplest and most economical methods, where, as here, but little need be removed, is to cement out the copper. A metal which will not contaminate the nickel and/ or cobalt products should be used for replacement. Nickel and/or cobalt produced in a prior cycle may be used. Any metal so used will be recovered in this cycle without loss. Copper removal, then, except as to the possible use of cobalt and/or nickel therein, also is not a necessary feature of the present process. If not required, it may be by-passed, as shown. Accordingly, it, too, has been shown in light lines.

The rst particular step in the process of the present invention is designated as a solution adjustment. This will include any necessary adjustment of the salt concentrations and proportions in solution and the acidic content of the liquor to obtain optimum initial conditions. However, instead of using conditions optimum for complete precipitation of metal, either cobalt or nickel, as when one is present as the only dissolved metal, the optimum conditions here must be favorable to cobalt retention and they must be maintained while precipitating nickel.

This solution adjustment must therefore accomplish a number of functions. First, it should insure so far as possible retaining the cobalt and nickel in solution until they are to be precipitated asmetals. Secondly, it should establish conditions under which selective gaseous reduction of nickel from cobalt can be initiated. Third, it should provide for continuing the nickel reduction once it is initiated. Fourth, it should provide for proper terminal conditions for the nickel reduction. Fifth, it should provide for substantially complete cobalt retention until and at terminal conditions.

As to keeping the nickel and cobalt from premature precipitation, several factors are important. The cobalt must be in solution at the end of the nickel reduction. The nickel, if precipitated before the gaseous reduction, is unlikely to be in the form of elemental nickel. Even if reduced to the latter state from suspension as a solid nickel compound, the product is apt to be in an unsatisfactory physical condition. Were is not for these factors, adjustment would simply be to those values at which the terminal conditions would be correct.

To accomplish the intended results of the solution adjustment then, it is necessary to do several things. First, the acidity must be adjusted to provide a minimum hydrogen ion content at which cobalt is not normally gas reducible. Secondly, since this will correspond to an acid content higher than the limiting acid conditions at which (Ni++) ions are apparently reducible directly to elemental metal from solutions of a nickel salt in water, there must be added some material capable of forming a nickel complex, reducible at thehydrogen ion content necessary to keep cobalt in solution. Finally, it is necessary to provide some material capable of taking up the hydrogen ions foundv as elemental nickel is produced and thereby prevent the acidityy from becoming high enough to stop the reduction of nickel prematurely.

In the present discussion material added to assist in reducing the nickel will be referred to as a compatible electrolyte; that added for purposes ofy acidity control will be referred to as an acid-neutralizing agent.

In the present process, controlled conditions of acidity, initially, during reduction, and terminally are highly iml portant. Because the source of the solution may have been so varied, it will often contain an excessive amount of sulfuric acid, which must4 be neutralized. Alkalineearth metals are not suitable because of the insolubility of their sulfates. Alkali metal and ammonium hydroxides are highlysuitable. Ammonia, however, is the most practical since it either may be recovered as a saleable sulfate or easily recovered for reuse, whichever is preferable. For the generally encountered case, then, ammonia is the most desirable neutralizing agent. As such, it will be taken as illustrative.

The term compatible electrolyte as used herein is intended to designate an acid or a salt meeting several certain requirements. First, it must furnish an anion capable of forming a gas-reducible complexI with nickel. Secondly, it must be soluble in the solution without caus. ing a premature precipitation or crystallization of anydissolved component. This necessitates its being com-1 patible with all of the dissolved components. In the illustrative case of sulfates solutions sulfuric acid itself or salts formed in neutralizing an excess of it or sodium, potassium, and ammonium sulfates may serve the purpose. Although, as will be noted, other acids may be present, since sulfuric acid is the most used acid and ammonia the most useful neutralizing agent, ammonium sulfate will constitute the most practical electrolyte. It is readily available as needed since it is a normal product of the illustrative process.

The function of the electrolyte is not certain in view of this variety of suitable compounds. It may be that in the presence of the acid, an anion complex such as Me(A)z wherein Me is nickel or cobalt and An is the anion radical may form and be more easily reduced than the metal ion. It may be that the increase in anions in solution due to its presence is suchv that for the acid dissociation constants the anticipated increase in hydrogen ions cannot occur, i. e.,v most of the hydrogen ions formed during reduction are converted to a less dissociated ion or undissociated acid molecules. lt may be a combina tion of these and other factors. However, ammonium sulfate, as a salt of a dibasic acid which itself has a relatively low dissociation as to the rst hydrogen, appears Ato fit in all the categories.

It should be noted that the terminal conditions for any metal precipitation step in the present separation process are the critical conditions for that step. Accordingly, the solution adjustment is an adjustment made for the purpose of insuring the correct conditions when the metal precipitation approaches completion. Any adjustment is therefore to certain initial conditions which, with allowance for the formation of acid during metal reduction, produces the necessary end result.

Where, as here, more than one metal precipitation step will be used, there are several possibilities. The first solution adjustment step in some cases may be one which will allow for production of satisfactory terminal conditions at the end of all the precipitation steps. Preferably, however, it will be an adjustment calculated to produce the optimum conditions at the end of the first metal precipitation. In such cases further adjustments can be made between subsequent precipitation steps. It is also quite possible, particularly where a large quantity of metal is to be precipitated in the first precipitation step, to adjust the solution to good staring conditions and make a further adjustment during the step.

There will be little or no cobalt precipitation above about 1.5% free acid even when cobalt is present in large amounts. Nickel will precipitate completely for all practical purposes at any acidity up to about 1% acid and in decreasing yields up to about 5% acid. Although the lower the acidity the more complete the nickel removal, care must be taken to insure against premature cobalt precipitation in obtaining a good nickel yield. Accordingly, there is for any stated Ni:Co mol ratio in solution, some optimum condition of acidity which should be achieved for most complete nickel precipitation free of cobalt. m f

Not only is the Ni:Co ratio important in determining the optimum acidity but also as to several factors. Another, for example, is the metals concentration in the solution. It can be expressed readily as total grams per liter of Ni plus Co metal in solution. However, the optimum total will vary with the Ni:Co ratio in the solution. If the ratio is above 5:1, 50-60 grams per liter is about the optimum. This will decrease to about 40-45 grams at 1:1 ratios; 35-40 at 1:5 and about 30 at lower ratios. As will be discussed, ratios below about 1:10 will seldom be treated to obtain a first nickel precipitate as such a product would be very small, if not negligible.

Accordingly, in the solution adjustment step makeup,

i. e., metal sulfates and/or ammonium sulfate and/or ammonia and/or sulfuric acid and, if necessary, water are added to bring the solution to the desired optimums of acidity, concentration and proportions.

The next step may be designated as the first nickel precipitation. Herein, the solution, adjusted as noted above, is treated under reducing conditions. Temperatures above 250 F. are required and above about y300" F. are needed to complete the cycle in a reasonable time. On the other hand, excessive temperatures not only militate against cobalt retention but require the use of pressures above about 1000 pounds per sq. in. They are not necessary and unduly increase the apparatus requirements. Therefore, while temperatures up to about 500 F. may be used in these and subsequent cycles, about 300-400 F. is preferable in this step.

A reducing gas, to be suitable, must be non-sulfidizing. Hydrogen, carbon monoxide and mixtures of them may be used. Diluent inert gases do not harm except to unduly increase the requisite total pressures. If possible, they should be avoided. Carbon monoxide under the acidic conditions here forms carbon dioxide which dilutes the reducing gas and may limit the reaction. Hydrogen, Where available, is definitely preferable. It may be added above or below the liquid surface during treatment.

If uncontrolled, the acid content will rise during reduction. Since nickel reduction is slow above about one percent free acid content, it is best that some neutralizing agent be added during the solution adjustment if the original solution contains acid inexcess of these amounts. On the other hand, adding enough ammonia to insure a desirable final acid content would in many cases make the original acid content low enough to permit excessive coprecipitation of cobalt. In those circumstances, in addition to the reducing gas some neutralizing agent may be added `during reduction. While other agents may be used, ammonia again is usually preferable. Usually, therefore, at least some ammonia is added during reduction as is shown. However, since there is a possibility that none may be needed, the addition is shown as a dotted line.

Ammonia is preferably used as a gas. While aqua ammonia may be used, it reduces the apparatus capacity.

The total amount available should be such that at the end of the nickel reduction cycle, the acid content will be at the optimum cut-off1 value. As noted above, this is the optimum acid content at which maximum-nickel minimum-cobalt precipitation occurs. Like the optimum metal concentration, the cut-olf acidity will vary with the original Ni:Co mol ratio. It varies in the range 0.2-1.0% acidity. From about 99% to 100% of the nickel at a 5:1 ratio or higher, and 95-99% at about 1:1 can be precipitated containing substantially no cobalt under these conditions. The nickel can be precipitated without an excessive cobalt content under these conditions. These figures, those previously given, and others, are summarized in the following Table I.

Reduction in this and subsequent steps may be either continuous or batchwise, using controlled content solutions and conditions. In batchwise operation a timed cycle may be used. For vany given solution a few trial runs will determine a time cycle which will stop reduction before the cobalt content of the nickel powderjbecomes sufficient to be uneconomical. For continuous operations, a few initial adjustments will establish the conditions at which the necessary solution feed rate may be maintained and the desired recovery obtained. In some cases, however, a particular mixture may be desired for making certain alloys. In that case, a higher cobalt content can be permitted up to the desired one.

The metal precipitate is filtered out, washed and dried, as shown. Any solids-liquid separation step may be substituted for the filtering operation. Washing and drying are conventional. Preferably, at least the finish of the drying should be carried out in 'a reducing atmosphere. The product will benickel in high purity.

The washings, while dilute, contain valuable materials. These are recovered as by recycling; crystallizing of the salts content and the like. These 4may be done in conventional manners and therefore their exact operations form no part of the present invention. v v

After removal of this product, in the illustrative case of Ni:Co ratios of about 1:1 and higher, the filtrate is sent to a cobalt reduction, as shown. Herein, under conditions ranging from those only slightly less acidic than in the first stage on into basic conditions, in a similar cycle, cobalt salt is reduced to cobalt metal in a nearly pure state, i. e., of a grade saleable as such.`

The acid content of the solution during this reduction should be less than 0.5% in any case. Preferably, it should be at a pH considerably higher than the cutoff value in the first reduction. Where ammonia is used, the solution may even be slightly basic, since at pHs above about neutrality, an ammine complex begins to fornil and reduction to Co metal can also be carried quite readily from that form. A temperature a little higher than for the nickel reduction is usually advantageous. Above about 300 F. is needed, above 350 F. is better and about 405 -4507 F. is a good practice. Temperatures above 500 F. may be used but are not needed. Apart from the unnecessarily high vapor pressure developed, solubilities of the cobalt salts decrease rapidly in the ncreasing temperature.

Cobalt powder is collected. washed and dried in a manner similar to the preceding product. The washings, too, are similarly processed. However, the filtrate, while substantially barren of cobalt and nickel, cannot be directly discarded because of its ammonium sulfate content. Therefore it is sent to some conventional circuit wherein ammonium sulfate is crystallized in some conventional manner as by water removal. The exact method of ammonia recovery or recycling is not a feature of the present invention and has not been shown.

Two different cases must be considered when it is desirable to extend the range of Ni:Co ratios which must be treated in the original feed sources. For Ni:Co mol ratios of from about 1:1 down to about 1:5, it is better to take the operation in three stages, as shown in the drawing.

For feed materials having these ratios, precipitation .of thezentire .-N i content: in the .first .stage swouldgusually resultain an :excessive .Cocontent therein. VA proper .dilution is-selected, 'usually not more than about V40 'grams-per `'liter of total Co plus Ni in solution. At the same vtimea,propercut-oii acidity value is selected, .usually between about 0.5%-1.0% sulfuric acid.

`flhis-solution is then subjected to a first nickel reduction. st eplmder similar conditions to those noted above. .'Reductiouis controlled by timing and/ or by controlling fthenendpoint acidity to some optimum cut-olf value, iusuallyrat or above the 0.5% at which all cobalt is retained. In any case, reduction is stopped before the .cobalt content in the product reaches the economically undesirable limit. This product is filtered, washed, dried, etc.,exactly`-as for the nickel product discussed above.

However, the filtrate, instead of passing to a cobalt precipitation, is sent to a second nickel reduction step. :This is indicated by the dotted line in the drawing. In `.this :second nickel reduction, the reducing conditions, ex- Aceptforthe degree of acidity, are like those of the irst stage. iHere, however, the final acidity is controlled to the point at which substantially all the Ni willfbe stripped from. solution with the optimum cobalt retention. This .acid concentration for differing metal ratios will also vary somewhat but will be close to the 0.5% value. End point control is preferably accomplished by adding NH3 tto thevnecessary degree preferably before raising the temperature. Reduction is then stopped and again the .product is collected, washed'and dried, as discussed above Vfor the first product. The residual solution, as shown. is sent to the cobalt reduction step where it is treated faswas discussed above.

A third type of situation is involved where the original NizCo mol ratios are from about 1:5 to 1:10 and lower. For such solutions, the process is again best carried out ,-5 EXAMPLE 1 A solution was prepared by. dissolving in'0`.2% 4aqueous 'sulfuricacid about 0.5 vparts'of ammonium sulfate'ard 0.75 part ofta crystal mixture of -cobalt and'nickelsulfates 'having a'nickehcobalt .mol ratioV of :about lil. '.'lhis lsolutionwas transferred to a stirred autoclave, `heated to about 400 'fF. and thepressure raisedto abouti800 jpounds per sq. in.'with hydrogen. ySutiicient NH3 to leave, 'after'reductiom about'0.5% free'acidwasnadded during reduction. After .about 'minutesftreatment stopped, the pressurerelievedand the solidsl collected. "No middling product was taken. Theiiltrate wasretreated under similar temperature andpressure conditions vafter neutralization Aof the free zacid ,Withzadde'd ammonia. In .the rst'product thenickelpowder'contained about 2.5% cobalt. Inthe second'about.97% of the original cobalt was obtained containing'ZlSU/o nickel. lBoth are saleable products, butl'bothV are* higher in'the other metal'than is completely satisfactory.

' EXAMPLE 2 Inorder to show the eiect of linal acid content an'd dilering NizCo ratios, the nickel precipitationstep .of Example 1 was repeated several times on similarcrystal mixtures of varyingNi:Co ratios. -Reduction was carried out to dilfering cut-off acid values. Reductionwas carried to the point at which the cobalt content ibecame about 0.5%. Illustrative -results l.are shown in Table II.

TABLE II in two=stages. For such concentrates, an attempt to take .af-first high-purity Ni product would, at best, yield only original N120., Content -Nipmduct -a-vsmalltuntity. lThe middlings or second sgage ilalrod- 011mm uct wo every arge iuproportiou. t is est. t ere- 4 acidity, fore, to take all the nickel as a middlines in the first 40 M01 Ram Gm'lLt' Asfyiee gnetr Ifema nickel reduction. .The low, however, will be much Percent VPercent .figs .the sameasthat shown in the drawingforthe first type NtzCo Ni vCo Orliml PCOdmt -ofy case. Tt is alsol noted in Table I. 1 ro uc Although -onlv two staaes .areused. all the nickel is .precipitated in the rst stage `and-the'moduct will be 45 1g 33'? g igg mired metal vasin the three-stage middlngs product 15 91 015 025 discussed vabove. The NitCo ratio in 'such products will 20 95 0.5 0:7 be some 3 to 10 times that in the original feed. Such gg gg g1g x l -a -mixedmeta uroductfon recycling, will'aive a good 33 (1)0 yieldl of purenickel in a'two-stage `or a three-stage, de-

-peridilie tuoon the NifCo ratio, operation such as has been discussed.

Since this product does correspond roughly to the middlingsproduct, reduction is carried out under the conditions therefor which lwere pointed out above. 'Reduction is carried toacut-of'f acidity at which substantially'all the nickel will have been reduced with a minimum cobalt content. 'This Vproduct is then removed and the residual solution treated for cobalt reduction, as al- Aready shownnd ,discussed TABLET 1 NOTE-At this ratio no attempt is made to obtain a nickelpioduct, all nickel being taken as a middling-see' Table' III.

EXAMPLE 3 The residual solutions obtained in the vlast six tests in Example 2 were stripped of nickel by similar reductions, carried to various end-point acid values. Illustrative'k results are shown in Table III. The cobaltfcontentf these middling products containing the residualnickel is indicated.

Effect of NizCo ratio on conditions and results 1st' Stage 2nd Stage 3rd Stage Gea. Nuon I. No. of

Ni & Co Percent Yield, Content, Content Yield 1 Ramo Salts Stages free (rlmrl Percent 'Percent (Percent Ni (Percent lergg (optimum) Acid at malt Ni in ist Ni in Ni in Mido0 in o0 Product Cut-Off 'e Stage Product dlings) Stage) U to 60.- 2 0. 20 2 99. 6 99. 5+ 96+ 2-5 'Uiito 5o..- 2 `0.13 .5 99. o 9am iNmB mkni 91 5 U t 40 3 0. 5-1.0 Il() 95 99.0* 0 r65-75 0.6 P 0 2 o. 5 .5 s?. 5 Arrr. o None teken. en -100 .2-5 Up to 40.-- 3 0. 5-1'. 0 l. 5-2. 0 70-80 97. 0 10-40 60-80 5 `Up to 30-.- 2 0. `l-. 5 .2 80-90 3 25)-40 50-70 5 1 Nora- Average percent of overall content before tirst reduction.

10 TABLE III It provides a method of selectively removing hydrogen, for example, from a gas mixture so that inert gases need Average Yleluy not be added to the pressure Vessel and lower total pres- O 1 C M Percent of Original sures may be used. In addition, by absorbing a definite Ema N1 01 Ram 5 amount it provides a control of the amount of metal Ni o precipitated.

Other electrolytes than ammonium sulfate may be em- Bd 0.8 ployed. These would include, as noted above, sulfates g l such. as the alkali metal sulfates and the alkali and am- 152 16' 27 0 monium salts of suitable acids, such as formic and acetic. 1:4 33 30 .So long as the hydrogen ion concentration and/ or activity 1:15 90 40 is kept from increasing, during metal reduction, without causing any extraneous precipitate, any compatible elec- EXAMPLE 4 15 trolyte as defined above may be used. The residual liquors from Example 3 were subjected to As noted above, the separation capabilities of a suitable a cobalt precipitation, as in Example l. Illustrative re- P'TOCCSS must @Xtnd the PlOduCtlOlJ 0f Cobalt and sults are shown in Table IV, nickel products containing less than 0.5% by weight of TABLE IV the other. The present process can be utilized to make products of this and better purity. The foregoing discus- Average Average sions have established the necessary conditions to obtain Yield, Content, Such results', l originel Nizoo Moi Ratio Percent Percent However, in some cases it may be permissible, provided af Plduuct the market is available, or for reason of economy on difficult concentrates to produce products of lesser purities. 3.1 94 0 5 In such cases the NisCo ratio is still important. However, 221' 80 the optimum cut ofi acid values, i. e., the hydrogen ion lll control, need not be so strictly limited. The eiect of such 124; 69 30, variations on some materials may be illustrated as in the 1:15-. 59 following Table V. Such figures must, however, be approximations due to concentration variations for the var- Although it does not form part of the present invention, IOUS POSSlble Solutes.

TABLE V First step nickel reduction P it erccnt Co in Ni) and yield of Ni reduction ercent vx. Terminal acid Ougmal Solution UI Y (p concentration (percent HZSOEJ) .5% Co iii Ni 1% Co in Ni 2.5% C5 in Ni 5% Oo in Nl M01 Ratio N1 0 Nizoo Hisoi, Yield, Hisoi, Yield, Hisoi, Yield, Hisoi, Yield, Percent Percent Percent Percent Percent Percent Percent Percent e 1 i5 (100) 12 (100) 0s lloc) 03 100) 9 2. 25 (100) 23 (100) 20 100) 17 100) 20 .70 05 .58 (Q5-95) .66 (Q5-95) .60 95 2s (l.0-l) 40-45 (1.0-) 40-50 not possible not possible not possible not possible Norm-When it makes no sense to indicate higher accuracy, gures are put in brackets. 1 Even at .30% acidity 100% of Ni precipitated, but at higher purity.' 2 At .40% acidity, no cobalt should yet be precipitated up to 0.5 gr Ni/lt. may beleft unreduced. use of seed metal powder in the metal precipitation steps Inorder to obtain in the last step by strippingthe is highly advantageous. Its effect is definite, somewhat solution' l00% cobalt powder of the following nickel catalytic, even though its mode of operation is uncertain. content in the lndicated yield, the previous reduction step A good yield with no tendency to foil formation and (1st or 2nd middluig) has to terminate at the acid condeposition on the vessel is obtained. centrations shown in the following table:

TABLE VI Third step Co reduction u Original solution .5% Ni in Co 1% Ni in Co 2.5% Ni in Co 5% Ni in Oo Moi Ratio 00u/larg' Hisoi, yield, H2504, yield, H2504, yield, mso., yield,

NzCo glglizco Percent Percent Percent Percent Percent Percent Percent Percent e 0.30 (10o) o. 40 (100) 0. 45 (100g 0. 50 (100) 45 9 0. 40 (100) 0. 45 (100) 0. 50 (100 0. 55 (100) 20 2o (0.45) 75+ (0.50) 80+ 0.55) 85+ 0. 65 (Q5-10o) 4 28 (0.45) 50-75 (0.50) Eesti-50) 0.55) (7o-90) 0.70 9o 1.5 30 (0.45) 50-70 (0.50) 50-75) 0.55) 65-80 .75 (so) Use of powder is particularly helpful the case of I claim: nickel. When used, it should be finely divided, below 40 l. In the hydrornetallurgical separation of high-purity mesh and preferably below about 150 mesh. cobalt from substantially copperand iron-free acidic It may be used in large amounts, since it represents solutions containing cobalt and nickel; the steps of: adno loss. As much should be used as is convenient, up to lusting the hydrogen lon concentration to acidic condithe amount which can be well dispersed and suspended tions less than that equivalent to about a free acid conby the agitator with which the vessel should be equipped. tent of 5%; heating adjusted solution, to temperatures This may be a weight equal to the amount of metal preabove about 250 F., in the presence of a non-sulfidizing cipitated or even several times this Weight. A useful reducing gas and a compatible electrolyte the anion of possibility lies in using it to absorb the reducing gas before which is capable of forming a gas-reducible anion comactual metal reduction. This serves two useful functions. plex with nickel ions whereby nickel is reduced to nickel metal; continuing the reductionin the presence of a. sucient amount of a soluble-salt-forming acid-neutralizing agent to produce, after, reduction, a hydrogen ion concen: tration ranging from thatl equivalent to afree acid con` tent of from about (l1-0.2% for original Ni:Co mol ratios of about :1 and higher to that of aboutra 1.0% solution for original NizCo ratios `of- 1:1 to 1:10, until nickel precipitation substantially ceases and removing precipitate, whereby a solution suitable for cobalt metal precipitation, is obtained.

2. A process according to clairn linwhich the solution, after said initial Ahydrogen ion adjustment, contains at least 0.2 mols per literof ammonium sulfate.

3. A processaccording--to-claim 1 inV which the acid is sulfuric.

4. A process according-toclaim-l '-inwhich neutralizing agent is ammonia.-

5. A process `according to claimA 1 iin which the soluble salt formed. is ammonium sulfate.

6. A process-accordingto claiml yin. which acid is sulfuric, the neutralizingagent. is ammonia and the soluble salt formed is ammonium sulfate.

7. In the hydrometallurgicalz. separation of high-purity nickel and cobalt from substantially copperand iron-free acidic solutions containingnickel andcobalt in the `mol ratios of from aboutf3z`l tol about 1:5,' the steps of:` adjusting thehydrogen ion concentration to Vacid conditions less than that equivalent toabout'a freeacid content of 5%; heating-the-adjusted solution;tovtemperaturesl above about 250i Ff., inthepresenceoffa non-suldizing reducingfgas anda compatibleelectrolyte the anion of which` is -capableof forming-a gas-reducible anion` complex with nickel ions whereby nickel is reducedsto;metallicnickel;; continuing the reduction in the presenceofa suicient amount of a soluble salt-forming acid-neutralizing agent to produce, after reduction, a .hydrogenioni-concexzltrae` tionY equivalent-to--afvfree-acid content-ot about 0.5 continuing the reduction ,.,untiLfnickel fpreciptationr-subf stantially ceases; collecting; precipitatel as high-grade nickel product; again heating the residual'solutionunden substantially` similar lreducing` conditions luntil. Inickel pre1v cipitation is substantial1y-comp1eteinthe presence-ofA the. increased amountV of acid-neutralizing agent-asucient to reduce the hydrogenv ion-content^s after reduction; to that equivalent of from a free acid Vcontentof 'about 012%" for a 1:1 ratio toaboutthat of adfree acidcontent-.fof about 0.3% for a ,1:5-and lower ratidand removingjany precipitate; whereby asolution Asuitable. for` cobalt?. metal precipitation is obtained."

S. A process according to claim 7 in which the solution,l

after adjustment, contains atleastt2molfper'liter of' ammoniumsulfate.

9. A process accordingctorclim 7 in which acid is sulfuric.

10., A process taccording to claim 7 in which neutralizing .agent 1s ammonia 11... A processv according to claim 7-fin'whih` the soluble salt materialis ammonium sulfate.

l2. Ar p rocessfaccordngyto claim 7 in which the acid is sulfuric, the neutralizing agent is ammonia and the soluble salts ammonium'su'lfate:

13. In the hydrometallurgical.separation of highpurityf` nickel containing not -morethan about 2.5 cobaltfromt substantially. copper-Y andv iron=free "acidic-solutions com. taining nickel andcobalt in molratios of `about 1':`l` and higher, the steps off adjiistingthe hydrogen io'n content to acidic conditions lessthanth'at equivalent to about a free:acid-content` of:5%1; iheatingt the-fadjustecltsolution, toftemperatures above( about 250? F:,.infthe-presence;of-: a nonsultidizing reducing gas anda'aicompatible.electrolyte: the anion of which is capableof -forming a gas-reducible anion complex with nickel ions whereby nickel is reduced to nickel metal in the presence of a su'ient amount of va solublersalt-forming acid-neutralizing agent to produce, after reduction,A a hydrogen, ion. contennot less.than that equivalenttoy arlee acid content of about 0.5%r for a 1:1

. ratio'down'tonabout neutral conditions for a 20:1 ratio;

` continuing-the reductiorruntil-nickel-precipitation-substanA SOL tially ceases and collecting precipitated nickel.

14.` A* process according toV claim n13s .infwhichthesold#n tion, after; adjustment,- contains at least" 0.2'nrolsperliterr of Yammonium sulfate.`

15.- Aprocess zaccordingto `claim 13 --in -whichuacid'isl sulfuric.

16.1A process; accordingzto. claim..- 13. int :which` neutralizing agent is ammonia.

17. A process according to claim 13 in which the soluble salt formed is ammonium sulfate.

18. A process according to claim 13 in which the acid is sulfuric, the neutralizing agent is ammonia and the soluble salfformedzistammonium sulfate.

19.v A p rocess according to claim 13 in which the product contains not more than 0.5% cobalt and the hydrogen ion contents-range from that of a 0.7% acid solution o'r a alflzrato downtoabout a 0.1% acid solution for ratios ori-20 El and higher.

Number 

1. IN THE HYDROMETALLURGICAL SEPARATION OF HIGH-PURITY COBALT FROM SUBSTANTIALLY COPPER- AND IRON-FREE ACIDIC SOLUTIONS CONTAINING COBALT AND NICKEL; THE STEPS OF: ADJUSTING THE HYDROGEN ION CONCENTRATION TO ACIDIC CONDITIONS LESS THAN THAT EQUIVALENT TO ABOUT A FREE ACID CONTENT OF 5%; HEATING ADJUSTED SOLUTION, TO TEMPERATURES ABOVE ABOUT 250* F., IN THE PRESENCE OF A NON-SULFIDIZING REDUCING GAS AND A COMPATIBLE ELECTROLYTE THE ANION OF WHICH IS CAPABLE OF FORMING A GAS-REDUCIBLE ANION COMPLEX WITH NICKEL IONS WHEREBY NICKEL IS REDUCED TO NICKEL METAL; CONTINUING THE REDUCTION IN THE PRESENCE OF A SUFFICIENT AMOUNT OF A SOLUBLE SALT-FORMING ACID-NEUTRALIZING AGENT TO PRODUCE, AFTER REDUCTION, A HYDROGEN ION CONCENTRATION RANGING FROM THAT EQUIVALENT TO A FREE ACID CONTENT OF FROM ABOUT 0.1-0.2% FOR ORIGINAL NI:CO MOL RATIOS OF ABOUT 5:1 AND HIGHER TO THAT OF ABOUT A 1.0% SOLUTION FOR ORIGINAL NI:CO RATIOS OF 1:1 T 1:10, UNTIL NICKEL PRECIPITATION SUBSTANTIALLY CEASES AND REMOVING PRECIPITATE, WHEREBY A SOLUTION SUITABLE FOR COBALT METAL PRECIPITATION IS OBTAINED. 